OCR (A) Chemistry A-level. Module 6: Organic Chemistry and Analysis

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1 OCR (A) Chemistry A-level Module 6: Organic Chemistry and Analysis Organic Synthesis Notes by Adam Robertson

2 DEFINITIONS Heterolytic fission: The breaking of a covalent bond when one of the bonded atoms takes both of the electrons. Homolytic fission: The breaking of a covalent bond when each of the bonded atoms takes one electron. Addition reaction: Two reactants join together to form one product. Substitution reaction: Two reactants where one atom or group of atoms replaces another set of atoms. Elimination reaction: A reaction which involves the removal or a small molecule from a larger one Electrophile: An atom or compound that are electron pair acceptors Nucleophile: An atom or compound that are electron pair donors REACTIONS COMBUSTION Requires heat For complete combustion there must be adequate levels of oxygen Complete: C 6 H O 6CO H O Incomplete: C 6 H O 6CO + 7H 2 O C H O 6C + 7H 2 O 2 1 2

RADICAL SUBSTITUTION In presence of ultraviolet light Three steps : initiation, propagation and termination Since the reaction is uncontrollable and can be very unstable, it is typically not used in

3 RADICAL SUBSTITUTION In presence of ultraviolet light Three steps : initiation, propagation and termination Since the reaction is uncontrollable and can be very unstable, it is typically not used in synthesis. In addition several products are made rather than just desired products In this scenario CHLOROMETHANE can go on to react with another chlorine radical which will substitute another hydrogen atom creating DICHLOROMETHANE. Further substitution can occur to form TRICHLOROMETHANE and TETRACHLOROMETHANE substitution can also happen at any point on the carbon chain, leading to a low yield of a specific product HYDROGENATION At 423K Nickel catalyst

4 HALOGENATION How alkenes decolourise bromine water (orange-brown colourless) Occurs at room temperature an electrophilic addition reaction HYDRATION an alkene is reacted with steam phosphoric acid catalyst (H 3 PO 4 ) if the alkene is unsymmetrical, a mixture of products is formed Addition reactions of alkenes with hydrogen halides conditions: room temperature reactant: hydrogen halide if the alkene is a gas, the two gases are mixed. If the alkene is a liquid, the hydrogen halide is bubbled through electrophilic substitution reaction if the alkene is unsymmetrical, a mixture of products will be formed alkene + hydrogen halide haloalkane

5 ELECTROPHILIC ADDITION As with all of the reactions on this page, if the reactants allow it then two potential products can be formed. In order to find the major product we employ MARKOWNIKOFF S RULE which states that the higher yield product is the more stable product with the larger amount of R groups, e.g. a primary product will be less stable than a secondary product therefore there will be less of that primary product ADDITION POLYMERISATION (YR1) Nickel catalyst Very high temperatures and pressure OXIDATION OF ALCOHOLS Both reactions require acidified potassium dichromate (works as an oxidising agent) Gentle heating Primary alcohols oxidise to form aldehydes and carboxylic acids: o under distillation + gentle heating: alcohol + [O] aldehyde + H 2 O

6 o under reflux + strong heat, excess K 2 Cr 2 O 7 : alcohol + 2[O] carboxylic acid + H 2 O Secondary alcohols oxidise to form ketones: o alcohol + [O] ketone + H 2 O DEHYDRATION OF ALCOHOLS Heated under reflux Requires sulfuric or phosphoric acid H 2 O SUBSTITUTION OF ALCOHOLS Heat under reflux in the presence of sulfuric acid Reactants: sulfuric acid + sodium halide (forms hydrogen halide in situ e.g. NaBr + H 2 SO 4 NaHSO 4 + HBr) N abr + H 2 SO 4 NaHSO 4 + H Br C 3 H 7 OH + HBr C3H7 Br + H 2 O alcohol + HBr bromoalkane + H 2 O

7 NUCLEOPHILIC SUBSTITUTION OF HALOALKANES/HYDROLYSIS Requires a source of OH ions (usually from NaOH) nucleophilic substitution reaction heated under reflux to get a good yield reaction: o bromoalkane + NaOH alcohol + NaBr + - o bromoalkane + H 2 O alcohol + H + Br Speed of hydrolysis is relevant to bond strength of C X e.g: C Cl reacts slower than C I because C Cl has the stronger bond (more bond enthalpy RADICAL SUBSTITUTION OF OZONE LAYER INITIATION: CF 2 Cl 2 CF 2 Cl + C l PROPAGATION: C L + O 3 CLO + O 2 C lo + O Cl + O 2 overall: O 3 + O 2O 2 NITRATION OF BENZENE Reaction happens at 50 with a concentrated sulfuric acid catalyst to form nitrobenzene Above 50 the product formed will be 1,3 dinitrobenzene electrophilic substitution reaction

The reactant is concentrated nitric acid SO NO SO O HNO 3 + H 2 4 2 + + H 4 + H 2 H + + HSO H SO 4 2 4 HALOGENATION OF BENZENE conditions: room temperature + pressure Requires a halogen carrier since

8 The reactant is concentrated nitric acid SO NO SO O HNO 3 + H H 4 + H 2 H + + HSO H SO HALOGENATION OF BENZENE conditions: room temperature + pressure Requires a halogen carrier since benzene is too stable Halogen carriers are either FeX or AlX electrophilic substitution reaction H + + F ebr4 F ebr3 + H Br ALKYLATION OF BENZENE Benzene is reacted with a haloalkane Requires an aluminium chloride (AlCl 3 ) catalyst electrophilic substitution reaction

9 ACYLATION OF BENZENE benzene is reacted with an acyl chloride Requires an aluminium chloride (AlCl 3 ) catalyst Electrophilic substitution reaction NEUTRALISATION OF PHENOL Phenol is more electronegative than benzene Phenol acts as a weak acid only reacting with the stronger bases HALOGENATION OF PHENOL Room temperature Electrophilic substitution reaction white ppt is formed and bromine is decolourised NITRATION OF PHENOL At room temperature Reactant is dilute HNO 3 electrophilic substitution reaction a mixture of 2 products is formed

10 BROMINATION OF PHENYLAMINE rapid reaction speed, because NH 2 group activates the ring phenylamine + 3Br 2 2,4,6-tribromophenylamine + 3HBr BROMINATION OF NITROBENZENE a slow reaction because the NO 2 group deactivates the ring requires a halogen carrier and a high temperature nitrobenzene + Br 2 3-bromo,1-nitrobenzene + HBr REDUCTION OF THE CARBONYL WITH NABH 4 (NUCLEOPHILIC ADDITION) NaBH 4 is used as the reducing agent The reducing agent and the carbonyl are warmed in aqueous solution aldehyde reaction: aldehyde + 2[H] primary alcohol ketone reaction: ketone + 2[H] secondary alcohol

REDUCTION OF CARBONYL COMPOUNDS WITH HCN Hydrogen cyanide is very toxic, therefore sodium cyanide and sulfuric acid are used to provide the hydrogen cyanide safely for the reaction in the lab It is

11 REDUCTION OF CARBONYL COMPOUNDS WITH HCN Hydrogen cyanide is very toxic, therefore sodium cyanide and sulfuric acid are used to provide the hydrogen cyanide safely for the reaction in the lab It is useful for increasing the length of the carbon chain to establish different properties of a material The mechanism is the same as above however the H(-) ion is replaced with a CN(-) ion In this reaction water can be protonated or the O(-) can bond with a H(+) ion aldehyde/ketone + HCN hydroxynitrile (don t have to name these) OXIDATION OF ALDEHYDES ketones do not undergo oxidation 2- + aldehydes are heated under reflux with Cr 2 O 7 /H ions (usually from potassium dichromate and dilute sulfuric acid) aldehyde + [O] carboxylic acid this is the same as the reaction that takes place during the Tollen s Reagent test. The fact ketones don t undergo oxidation means that the Tollens test works. REDOX/NEUTRALISATION OF CARBOXYLIC ACIDS React in the same manner as other acids however they form a carboxylate salt reaction with metals: observations: metal disappears, effervescence of H 2 reaction with metal oxides or alkalis: H 2 O produced reaction with carbonates: H 2 O and CO 2 produced PREPARATION OF ACYL CHLORIDES Because of the toxic nature of the gas by-products, this reaction takes place in a fume cupboard + SOCl SO 2 + HCl

ESTERIFICATION OF CARBOXYLIC ACIDS The alcohol is warmed with a small amount of concentrated sulfuric acid ESTERIFICATION OF ACYL CHLORIDES The main difference here is that this form of

12 ESTERIFICATION OF CARBOXYLIC ACIDS The alcohol is warmed with a small amount of concentrated sulfuric acid ESTERIFICATION OF ACYL CHLORIDES The main difference here is that this form of esterification is irreversible and has the by-product of HCl instead of H 2 O reaction: acyl chloride + alcohol ester + HCl ACYL CHLORIDE AND PHENOL Unlike carboxylic acids, acyl chlorides and acid anhydrides are much more reactive which means they can form an ester with phenol ACID ANHYDRIDES AND PHENOL Acid anhydrides react in the same way as acyl chlorides however do not produce as toxic products and the reactions are typically more controlled, hence why they are preferred in the lab. They are formed from two carboxylic acids ACYL CHLORIDE TO CARBOXYLIC ACID acyl chlorides are reacted with water to produce a carboxylic acid

A violentreaction that takes place in a fume cupboard due to the HCl gas ACYL CHLORIDES TO FORM PRIMARY AMIDES Both ammonia and amines can act as nucleophiles by donating their lone pair of electrons

13 A violentreaction that takes place in a fume cupboard due to the HCl gas ACYL CHLORIDES TO FORM PRIMARY AMIDES Both ammonia and amines can act as nucleophiles by donating their lone pair of electrons from the nitrogen atom For a primary amide to be formed the reaction must take place with ammonia acyl chloride + 2NH 3 primary amide + NH 4 Cl FORM SECONDARY AMIDES In this reaction a primary amine replaces ammonia to form a secondary amide acyl chloride + primary amine secondary amide - + CH 3 NH 3 + Cl HYDROLYSIS OF ESTERS ACID Ester is heated under reflux with water and a dilute acid This reaction is reversible

14 ALKALINE Ester is heated under reflux but with hydroxide ions instead This reaction is irreversible AMINES AS BASES The lone pair of electrons on the nitrogen atom can accept a proton When a reaction takes place a dative covalent bond is formed 2- e.g. 2CH 3 NH 2 + H 2 SO 4 (CH 3 NH 3 + ) 2 SO 4 PREPARATION OF PRIMARY AMINES (NS) Reaction takes place with excess ammonia, which acts as the nucleophile due to its lone pair of electrons, and it also prevents further substitution into secondary and tertiary amines Ethanol is used as the solvent - CH 3 Cl + NH 3 CH 3 NH 3 + Cl haloalkane + NH 3 alkylammonium chloride - CH 3 NH 3 + Cl + NaOH CH 3 NH 2 + NaCl + H 2 O alkylammonium chloride + NaOH amine + NaCl + H 2 O PREPARATION OF SECONDARY AMINES - CH 3 Cl + CH 3 NH 2 (CH 3 ) 2 NH 2 + Cl haloalkane + primary amine dialkylammonium chloride - (CH 3 ) 2 NH 2 + Cl + NaOH (CH 3 ) 2 NH + NaCl + H 2 O dialkylammonium chloride + NaOH secondary amine + NaCl + H 2 O Further substitutions can take place to create tertiary and quaternary amines by reacting the secondary and tertiary amines in the same manner respectively

PREPARATION OF PHENYLAMINE Nitrobenzene is heated under reflux with tin and hydrochloric acid to form phenylammonium salt, which is then reacted with excess sodium hydroxide AMINO ACID PLUS ACID

15 PREPARATION OF PHENYLAMINE Nitrobenzene is heated under reflux with tin and hydrochloric acid to form phenylammonium salt, which is then reacted with excess sodium hydroxide AMINO ACID PLUS ACID Reacts to form a salt ALKALI AMINO ACID PLUS Reacts to form a salt with the carboxylic acid group (e.g. COO-Na+) and water ESTERIFICATION OF AMINO ACIDS conditions: heat and concentrated sulfuric acid catalyst + amino acid + alcohol + H ester + H 2 O CONDENSATION POLYMERISATION Form a polyester or polyamide by removal of a water molecule or HCl Forms an ester or amide linkage respectively For polyesters either a monomer with a carboxylic acid group and an alcohol group is required or two different monomers, one a diol (2 hydroxyl groups) and the other a dicarboxylic acid (2 carboxylic acids) For polyamides either a monomer with a carboxylic acid/acyl chloride group and an amine group is required or two different monomers, a dicarboxylic acid/acyl chloride and the other a diamine

16 HYDROLYSIS OF POLYESTERS Hot acid HYDROLYSIS OF POLYAMIDES Hot acid HALOALKANE TO NITRILE Used to lengthen the carbon chain It s a nucleophilic substitution reaction with either sodium/potassium cyanide as hydrogen cyanide is very poisonous the reaction occurs in ethanol

17 REDUCTION OF NITRILES Reduced to an amine with a nickel catalyst and hydrogen HYDROLYSIS OF NITRILES Form carboxylic acids when heated with dilute acid and water

Mechanisms. . CCl2 F + Cl.

Mechanisms. . CCl2 F + Cl. Mechanisms 1) Free radical substitution Alkane à halogenoalkane Initiation: Propagation: Termination: Overall: 2) Ozone depletion UV light breaks the C Cl bond releasing chlorine radical CFCl 3 F à. CCl2